EP0463400A1 - Transparents - Google Patents

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Publication number
EP0463400A1
EP0463400A1 EP91109012A EP91109012A EP0463400A1 EP 0463400 A1 EP0463400 A1 EP 0463400A1 EP 91109012 A EP91109012 A EP 91109012A EP 91109012 A EP91109012 A EP 91109012A EP 0463400 A1 EP0463400 A1 EP 0463400A1
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EP
European Patent Office
Prior art keywords
poly
comprised
percent
weight
styrene
Prior art date
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Granted
Application number
EP91109012A
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German (de)
English (en)
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EP0463400B1 (fr
Inventor
Shadi L. Malhotra
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Xerox Corp
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Xerox Corp
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/0013Inorganic components thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • G03G7/0026Organic components thereof being macromolecular
    • G03G7/0033Natural products or derivatives thereof, e.g. cellulose, proteins
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • G03G7/0026Organic components thereof being macromolecular
    • G03G7/004Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002Organic components thereof
    • G03G7/0026Organic components thereof being macromolecular
    • G03G7/0046Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0053Intermediate layers for image-receiving members
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/508Supports
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5236Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5245Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5263Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281Polyurethanes or polyureas
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258Alkali metal or alkaline earth metal or compound thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259Silicic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2839Web or sheet containing structurally defined element or component and having an adhesive outermost layer with release or antistick coating

Definitions

  • This invention relates generally to transparencies which, for example, are suitable for various printing processes such as ink jet, dot matrix, electrographic and xerographic imaging systems, including color systems. More specifically, the present invention is directed to transparencies with certain coatings thereover, which transparencies, that is for example transparent substrate materials for receiving or containing a toner image, possess compatibility with toner and ink compositions, and permit improved toner and ink flow in the imaged areas of the transparency thereby enabling images of high quality, that is for example images with optical densities of greater than 1.0 in several embodiments, excellent toner fix, about 100 percent in some instances, and no or minimized background deposits to be permanently formed thereon.
  • transparencies that is for example transparent substrate materials for receiving or containing a toner image, possess compatibility with toner and ink compositions, and permit improved toner and ink flow in the imaged areas of the transparency thereby enabling images of high quality, that is for example images with optical densities of greater than 1.0 in several embodiments, excellent toner
  • electrophotographic, especially xerographic, ink jet, dot matrix printers and the like transparencies, that is for example a transparency useful in xerographic apparatuses such as the Xerox Corporation 1025TM, the Xerox 1075TM, the Xerox Ink Jet 4020TM, and in dot matrix printers, such as the Roland PR-1012TM and the like comprised of a supporting substrate; and an ink or toner receiving coating composition on both sides of the substrate and comprised of an adhesive layer polymer such as chlorinated poly(isoprene), chlorinated poly(propylene), blends of phosphate esters with poly(styrene), and the like, and an antistatic layer on one, or both sides of the adhesive layer, which antistatic layer is comprised of complexes of metal halides such as potassium iodide, urea compounds such as urea phosphate,and the like, with polymers containing oxyalkylene units such as poly(
  • transparencies many different types are known, reference for example U.S. Patent 3,535,112, which illustrates transparencies comprised of a supporting substrate, and polyamide overcoatings. Additionally, there are disclosed in U.S. Patent 3,539,340 transparencies comprised of a supporting substrate and coatings thereover of vinylchloride copolymers. Also known are transparencies with overcoatings of Styrene acrylate or methacrylate ester copolymers, reference U.S. Patent 4,071,362; transparencies with blends of acrylic polymers and vinyl chloride/vinylacetate polymers as illustrated in U.S. Patent 4,085,245; and transparencies with coatings of hydrophilic colloids as recited in U.S. Patent 4,259,422.
  • the aforementioned coatings primarily contain amorphous polymers which usually do not undergo the desired softening during fusing of, for example, the electrographic, especially xerographic, image which is achieved in a time frame of from about 25 to about 50 milliseconds at a fuser roll temperature of about 175°C.
  • antistatic agents which are primarily quaternary ammonium salts such as alkylbenzyldimethyl compounds, ionic salts such as sodium chloride, nonionic surfactants such as alcohol ethoxylates, anionic surfactants such as the sodium salt of sulfated alcohols, cationic surfactants such as amine ethoxylates, electroconductive polymers such as poly(styrene sulfonic acid) sodium salt, and these antistatic agents are not believed to assist in toner fix as they have neither sharp melting points, which are desirable, nor affinity for the hydrophobic xerographic toners.
  • antistatic agents which are primarily quaternary ammonium salts such as alkylbenzyldimethyl compounds, ionic salts such as sodium chloride, nonionic surfactants such as alcohol ethoxylates, anionic surfactants such as the sodium salt of sulfated alcohols, cationic surfactants such as amine ethoxylates, electroconductive polymers
  • the ink or toner receiving layer contains ionic or nonionic surfactants alone as antistats
  • their concentrations in the mixture approach as high as 30 percent or even more to be effective for xerographic imaging which requires that the transparency accept charge of between 100 to 400 volts and discharge instantaneously under light.
  • the adhesion of toner to the transparency is usually poor and not acceptable.
  • a feature thereof is to minimize the quantities of the oxyalkylene containing antistatic ionic and nonionic polymers, which is achieved by improving their efficiency by complexing them with metal halides such as potassium iodide, sodium iodide, zinc chloride, magnesium chloride, lithium bromide, cadmium chloride and urea compounds, and then using them as antistatic agents.
  • metal halides such as potassium iodide, sodium iodide, zinc chloride, magnesium chloride, lithium bromide, cadmium chloride and urea compounds
  • metal halides such as potassium iodide with oxyalkylene units containing polymer such as poly(ethylene oxide) are also elastomeric in nature and assist in better toner fix as well as act as antistatic agents even at very low humidity such as 10 percent relative humidity.
  • Conventional antistatic agents such as salts usually fail under these conditions.
  • 4,711,816 relating to, for example, a transparency sheet material with four layers, see column 2, line 30, and more specifically a prime coat layer with antistatic agents such as polyoxyethylene derivatives, polyglycols, and the like, see column 3; an image receiving layer of, for example, cellulosics, vinyl acetate, acrylonitrile-butadiene-styrene, see columns 3 and 4; and a protective layer of suitable resins such as polyesters; and as background interest 3,861,942; 4,013,696 and 4,480,003.
  • transparency sheet materials for use in a plain paper electrostatic copiers comprising (a) a flexible, transparent, heat resistant, polymeric film base, (b) an image receiving layer present upon a first surface of the film base, and (c) a layer of electrically conductive prime coat interposed between the image receiving layer and the film base.
  • This sheet material can be used in either powder-toned or liquid-toned plain paper copiers for making transparencies, reference U.S. Patent 4,711,816, the disclosure of which is totally incorporated herein by reference.
  • Patent 4,234,644 the disclosure of which is totally incorporated herein by reference, there is disclosed a composite lamination film for electrophoretically toned images deposited on a plastic dielectric receptor sheet comprising in combination an optically transparent flexible support layer, and an optically transparent flexible intermediate layer of a heat softenable film applied to one side of the support; and wherein the intermediate layer possesses adhesion to the support.
  • thermoplastic resins having a glass transition temperature of from a minus 50 to 150°C, such as acrylic resins, including ethylacrylate, methylmethacrylate, and propyl methacrylate; and acrylic acid, methacrylic acid, maleic acids, and fumaric acid, reference column 4, lines 23 to 65.
  • thermoplastic resin binders other than acrylic resins can be selected, such as styrene resins, including polystyrene, and styrene butadiene copolymers, vinyl chloride resins, vinylacetate resins, and solvent soluble linear polyester resins.
  • styrene resins including polystyrene, and styrene butadiene copolymers
  • vinyl chloride resins vinylacetate resins
  • solvent soluble linear polyester resins solvent soluble linear polyester resins.
  • Suitable materials for the image receiving layer include polyesters, cellulosics, poly(vinyl acetate), and acrylonitrile-butadiene-styrene terpolymers, reference column 3, lines 45 to 53.
  • Similar teachings are present in U.S. Patent 4,599,293, wherein there is described a toner transfer film for picking up a toner image from a toner treated surface, and affixing the image, wherein the film contains a clear transparent base and a layer firmly adhered thereto, which is also clear and transparent, and is comprised of the specific components as detailed in column 2, line 16.
  • Suitable binders for the transparent film include polymeric or prepolymeric substances, such as styrene polymers, acrylic, and methacrylate ester polymers, styrene butadienes, isoprenes, and the like, reference column 4, lines 7 to 39.
  • the coatings recited in the aforementioned patent contain primarily amorphous polymers which usually do not undergo the desired softening during the fusing of the xerographic imaging processes such as the color process utilized in the Xerox Corporation 1005TM, and therefore these coatings do not usually aid in the flow of pigmented toners. This can result in images of low optical density which are not totally transparent.
  • Patent 4,547,405 describes an ink jet recording sheet comprising a transparent support with a layer comprising 5 to 100 percent by weight of a coalesced block copolymer latex of poly(vinyl alcohol) with polyvinyl(benzyl ammonium chloride), and 0 to 95 percent by weight of a water soluble polymer selected from the group consisting of poly(vinyl alcohol), poly(vinyl pyrrolidone), and copolymers thereof.
  • a support is also disclosed in the '405 patent, which support may include polycarbonates, see column 4, line 62, for example. The disclosures of each of the aforementioned patents are totally incorporated herein by reference.
  • U.S. Patent 4,680,235 there is disclosed an ink jet recording material with image stabilizing agents, see column 4, lines 32 to 58, for example. Also, in column 4, line 57, for example, this patent discloses the use of a plasticizer in a surface recording layer. Further, in U.S. Patent 4,701,837 there is disclosed a light transmissive medium having a crosslinked polymer ink receiving layer; and U.S. Patent 4,775,594 describes an ink jet transparency with improved wetting properties.
  • coatings for ink jet transparencies include blends of carboxylated polymers with poly-(alkylene glycol), reference U.S. Patent 4,474,850; blends of poly(vinyl pyrrolidone) with matrix forming polymers such as gelatin; or poly(vinyl alcohol), swellable by water and insoluble at room temperature but soluble at elevated temperatures, reference U.S. Patent 4,503,111; and blends of poly(ethylene oxide) with carboxymethyl cellulose as illustrated in U.S. Patent 4,592,954, mentioned herein, the disclosure of each of the aforementioned patents being totally incorporated herein by reference.
  • Patent 4,592,954 is their insufficient resistance to relative humidities of, for example, exceeding 50 percent at 80 F which leads to the onset of blooming and bleeding of colors in the printed text or graphics only in four to six hours. These and other disadvantages are avoided or minimized with the transparencies of the present invention in embodiments thereof.
  • ink jet transparencies comprised of a supporting substrate and thereover a blend comprised of poly(ethylene oxide) and carboxymethyl cellulose together with a component selected from the group consisting of (1) hydroxypropyl cellulose; (2) vinylmethyl ether/maleic acid copolymer; (3) carboxymethyl hydroxyethyl cellulose; (4) hydroxyethyl cellulose; (5) acrylamide-acrylic acid copolymer; (6) cellulose sulfate; (7) poly(2-acrylamido-2-methyl propane sulfonic acid); (8) poly(vinyl alcohol); (9) poly(vinyl pyrrolidone); and (10) hydroxypropyl methyl cellulose.
  • transparencies suitable for electrographic and xerographic imaging comprised of a polymeric substrate with a toner receptive coating on one surface thereof, which coating is comprised of blends of poly(ethylene oxide) and carboxymethyl cellulose; poly(ethylene oxide), carboxymethyl cellulose and hydroxypropyl cellulose; poly(ethylene oxide) and vinylidene fluoride/hexafluoropropylene copolymer, poly-(chloroprene) and poly(a-methylstyrene); poly-(caprolactone) and poly(a-methylstyrene); poly-(vinylisobutylether) and poly(a-methylstyrene); blends of poly(caprolactone) and poly(p-isopropyl a-methylstyrene); blends of poly(1,4-butylene adipate) and poly(a-methylstyrene); chlorinated poly-(propy
  • transparencies suitable for electrographic and xerographic imaging processes comprised of a supporting polymeric substrate with a toner receptive coating on one surface thereof comprised of (a) a first layer coating of a crystalline polymer selected from the group consisting of poly-(chloroprene), chlorinated rubbers, blends of poly-(ethylene oxide), and vinylidene fluoride/hexafluoropropylene copolymers, chlorinated poly(propylene), chlorinated poly(ethylene), poly(vinylmethyl ketone), poly(caprolactone), poly-(1,4-butylene adipate), poly(vinylmethyl ether), and poly(vinyl isobutylether); and (b) a second overcoating layer comprised of a cellulose ether selected from the group consisting of hydroxypropyl methyl cellulose, hydroxy
  • a transparency comprised of a hydrophilic coating and a plasticizer, which plasticizer can, for example, be selected from the group consisting of phosphates, substituted phthalic anhydrides, glycerols, glycols, substituted glycerols, pyrrolidinones, alkylene carbonates, sulfolanes, and stearic acid derivatives.
  • plasticizer can, for example, be selected from the group consisting of phosphates, substituted phthalic anhydrides, glycerols, glycols, substituted glycerols, pyrrolidinones, alkylene carbonates, sulfolanes, and stearic acid derivatives.
  • a transparent substrate material for receiving or containing an image comprising a supporting substrate base, an antistatic polymer layer coated on one or both sides of the substrate and comprised of hydrophilic cellulosic components, and a toner receiving polymer layer contained on one or both sides of the antistatic layer, which polymer is comprised of hydrophobic cellulose ethers, hydrophobic cellulose esters or mixtures thereof, and wherein the toner receiving layer contains adhesive components.
  • an imaged transparency comprised of a supporting substrate, oil absorbing layer comprised of, for example, chlorinated rubber, styrenediene copolymers, alkylmethacrylate copolymers, ethylene-propylene copolymers, sodium carboxymethyl cellulose or sodium carboxymethylhydroxyethyl cellulose; an ink receiving polymer layer comprised of, for example, vinyl alcohol-vinyl acetate, vinyl alcohol-vinyl butyral or vinyl alcohol- vinylacetate-vinyl chloride copolymers.
  • the ink receiving layers may include therein or thereon fillers such as silica, calcium carbonate, titanium dioxide.
  • a never-tear coated paper comprised of a plastic supporting substrate, a binder layer comprised of polymers selected from the group consisting of (1) hydroxypropyl cellulose, (2) poly(vinyl alkyl ether), (3) vinyl pyrrolidone-vinyl acetate copolymer, (4) vinyl pyrrolidone-dialkylamino ethyl methacrylate copolymer quaternized, (5) poly(vinyl pyrrolidone); (6) poly(ethylene imine), and mixtures thereof; and a pigment or pigments; and an ink receiving polymer layer.
  • a binder layer comprised of polymers selected from the group consisting of (1) hydroxypropyl cellulose, (2) poly(vinyl alkyl ether), (3) vinyl pyrrolidone-vinyl acetate copolymer, (4) vinyl pyrrolidone-dialkylamino ethyl methacrylate copolymer quaternized, (5) poly(vinyl pyr
  • transparencies for ink jet printing processes and xerographic printing processes which transparencies are comprised of a supporting substrate and a coating composition thereon comprised of a mixture selected from the classes of materials comprised of (a) nonionic celluloses such as hydroxyl- propylmethyl cellulose, hydroxyethyl cellulose, hydroxybutyl methyl cellulose, or mixtures thereof; (b) ionic celluloses such as anionic sodium carboxymethyl cellulose, anionic sodium carboxymethyl hydroxyethyl cellulose, cationic celluloses, or mixtures thereof; (c) poly(alkylene oxide) such as poly-(ethylene oxide) together with a noncellulosic component selected from the group consisting of (1) poly(imidazoline) quaternized; (2) poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride); (3) poly(2-acrylamido-2-methyl propane sulfonic acid); (4) poly(ethylene
  • the aforementioned coating compositions are generally present on both sides of a supporting substrate, and in one embodiment the coating is comprised of nonionic hydroxyethyl cellulose, 25 percent by weight, anionic sodium carboxymethyl cellulose, 25 percent by weight, poly(ethylene oxide), 25 percent by weight, and poly(acrylamide), 25 percent by weight. Also, the coating can contain colloidal silica particles, a carbonate, such as calcium carbonate, and the like primarily for the purpose of transparency traction during the feeding process.
  • the coating composition can thus be comprised of a mixture of nonionic hydroxyethyl cellulose, 25 percent by weight, nonionic hydroxypropyl methyl cellulose, 20 percent by weight, anionic sodium carboxymethyl cellulose, 20 percent by weight, poly(ethylene oxide), 20 percent by weight, acrylamide-acrylic acid copolymer, 12 percent by weight, and colloidal silica, 3 percent by weight.
  • a transparent substrate material for receiving or containing an image comprised of a supporting substrate and a coating composition comprised of a mixture of (a) nonionic celluloses and blends thereof; (b) ionic celluloses and blends thereof; (c) poly(alkylene oxide); and an additional non cellulosic component selected from the group consisting of (1) poly(imidazoline) quaternized; (2) poly-(N,N-dimethyl-3,5-dimethylene piperidinium chloride); (3) poly(2-acrylamido-2-methyl propane sulfonic acid); (4) poly(ethylene imine) epichlorohydrin; (5) poly(acrylamide); (6) acrylamide-acrylic acid copolymer; (7) poly(vinyl pyrrolidone); (8) poly(vinyl alcohol); (9) vinyl pyrrolidone-diethyl aminomethyl methacrylate copolymer quaternized; (10) vinyl pyr
  • transparencies illustrated in the prior art are suitable in most instances for their intended purposes, there remains a need for new transparencies with coatings thereover, which transparencies are useful in electrophotographic and xerographic imaging processes, and that will enable the formation of images with high optical densities. Additionally, there is a need for transparencies which permit improved ink and toner flow in the imaged areas thereby enabling high quality transparent images with acceptable optical densities. There is also a need for transparencies that possess other advantages, inclusive of enabling excellent adhesion between the toned image and the transparency selected, and wherein images with excellent resolution and no background deposits are obtained.
  • transparencies with polymer coatings possessing a high degree of crystallinity and a sharp melting point enabling these coatings to effectively soften during fusing thereof, especially in xerographic imaging and printing apparatuses, and also permitting transparencies that can enhance toner flowability.
  • transparencies with certain coatings, which transparencies are useful in electrophotographic imaging processes, dot matrix printers and ink jet printers.
  • transparencies with certain coatings thereover enabling images thereon with high optical densities, and wherein increased toner flow is obtained when imaged, for example, with commercially available xerographic imaging apparatuses and ionographic printers, inclusive of printers commercially available from Delphax such as the Delphax S-6000.
  • Another feature of the present invention resides in imaged transparencies that have substantial permanence for extended time periods.
  • Another feature of the present invention resides in the provision of transparencies for xerographic or electrographic systems such as the Xerox Corporation 1005TM imaging apparatus, the Xerox Corporation 1005TM imaging apparatus, the Xerox Corporation 1025TM imaging apparatus, or the Xerox Corporation 1075TM imaging apparatus.
  • transparencies with, for example, blends of coatings on a supporting substrate.
  • coatings for electrophotographic, especially xerographic, transparencies which coatings in an embodiment are comprised of a hydrophilic/hydophobic segment with block copolymers of ethylene oxide/propylene oxide surfactants in combination with known binder polymers, such as cellulose acetate hydrogen phthalate, chlorinated rubber, hydroxy propyl methyl cellulose phthalate styrene butadiene, vinyl alcohol/vinyl acetate, cellulose acetate, ethyl cellulose, mixtures thereof in some instances, and the like.; one advantage of the aforementioned surfactants residing in their sharp melting point, in some instances enabling enhanced toner flowability; and further the coating is not of sufficient water solubility, and normally static build up on the transparencies is avoided or minimized.
  • binder polymers such as cellulose acetate hydrogen phthalate, chlorinated rubber, hydroxy propyl methyl cellulose phthalate styrene butadiene, vinyl alcohol/vinyl a
  • transparancies with coatings thereover there are provided xerographic transparencies with coatings thereover which are compatible with the toner compositions selected for development, and wherein the coatings enable substantially static free images thereon with acceptable optical densities to be obtained.
  • transparencies for xerographic printing processes which transparencies are comprised of a supporting substrate and an ink or toner receiving coating composition on the two exposed surfaces, or both sides of the substrate and comprised of an adhesive layer polymer such as chlorinated poly(isoprene), chlorinated poly-(propylene), blends of antistatic plasticizers such as, phosphate esters with poly(styrene) and the like, and an antistatic layer on each exposed surface of the adhesive layer which antistatic layer is comprised of complexes or mixtures of metal halides such as potassium iodide with polymers containing oxyalkylene units or segments, or urea compounds such as urea or urea phosphate with polymers containing oxyalkylene units such as poly(ethylene oxide), poly(propylene oxide), ethylene oxide/propylene oxide block copolymers, ethoxylated amines and the like, and an optional resin binder polymer such as poly(2-
  • Embodiments of the present invention include a transparency comprised of a supporting substrate such as polyester and an ink or toner receiving coating composition present on both sides of the substrate and comprised of an adhesive layer polymer such as poly(alkenes), halogenated poly-(alkenes), halogenated poly(dienes), styrene/isoprene copolymers, ethylene/vinyl acetate copolymer, styrene/isobutylene copolymers, ethylene/ethyl acrylate copolymers, styrene/ethylene butylene copolymers, styrene/ethylene oxide copolymers, E - caprolactone/ethylene oxide copolymers, ethylene sulfide/ethylene oxide copolymer, ethylene terephthalate/ethylene oxide copolymers; blends of from about 99 to about 50 percent by weight of (a) ethyl cellulose, ethyl hydroxyethyl cellulose,
  • a low molecular weight antistatic plasticizer selected from the group consisting of alkanol amides, amine ethoxylates, imidazolines, quaternized imidazolines, sodium dia-Ikyl sulfosuccinates, phosphate esters, and alkanolamide ethoxylates, which adhesives can be dissolved in a solvent such as toluene in a concentration of 0.25 to about 5 percent by weight; and an antistatic layer on both sides, for example on each side of the exposed adhesive layer, which antistatic layer is comprised of complexes or mixtures of metal halides such as potassium iodide, sodium iodide, lithium bromide, zinc chloride, magnesium chloride, mercuric chloride, cadmium chloride, and urea compounds such as urea, thiourea, urea monohydrochlor
  • Another embodiment of the present invention is directed to transparencies comprised of a supporting substrate such as polyester (Mylar) with a thickness of from about 50 to about 150 microns with a coating composition on both sides, or surfaces thereof comprised in an effective thickness of from, for example, about 1 to about 10 microns of an adhesive polymer such as chlorinated poly-(isoprene), and an antistatic layer on both sides, that is each of the exposed surfaces, a total of two, of the adhesive layer comprised in an effective thickness of from, for example, about 1 to about 5 microns of a mixture of complexes of metal halides such as potassium iodide or urea compounds, each with oxyalkylene unit containing polymers such as poly(ethylene oxide) and an optional resin binder polymer such as poly(2-hydroxyethyl methacrylate), hydroxypropylmethyl cellulose, the ratio of the oxyalkylene unit containing polymer to the metal halides or urea being in the range of from about 0.001 to about
  • adhesive polymers include poly(ethylene), Brookfield viscosity at 140°C, of between 40 to 6,000 CPS; poly(propylene), atactic Brookfield viscosity at 191°C ranging between 200 CPS to 4425 CPS, and a softening point between 121°C to 150°C, poly(1-butene), isotactic weight average molecular weight of between 185,000 and 570,000; chlorinated poly(ethylene) with a chlorine content between 25 and 75 percent by weight; chlorinated poly(propylene) with a chlorine content between 25 and 75 percent by weight; chlorosulfonated poly(ethylene) chlorine content between 25 and 75 percent by weight, and a sulfur content as chlorosulfone of between 0.5 to 1.65 percent by weight; chlorinated poly(isoprene) with a chlorine content from about 25 to about 75 percent by weight; poly(chloroprene) with a chlorine content between 25 to about 75 percent by weight and a Mooney viscosity between 40 and
  • the preferred adhesive layer polymers in embodiments of the present invention are comprised of chlorinated poly(isoprene), chlorinated poly(propylene), blends of poly(styrene) with low molecular weight antistatic plasticizers such as alkanol amide, blends of poly-(a-methyl styrene) with ethoxylated amines because of the excellent toner adhesion with the coating of these polymers and these are commercially available at lower costs in most instances.
  • Incorporation of the antistatic plasticizers in certain adhesive layers has at least a two fold effect in embodiments of the present invention: (a) promotion of poly(styrene) type coatings to adhere better to Mylar and (b) avoiding static build-up on the poly(styrene) based adhesvie layer thereby facilitating the application of the antistatic layer on the top of adhesive layer from a volatile flammable organic solvent such as methanol or acetone and preventing fire hazards when the undercoats (adhesive) and overcoats (antistatic layers) are being applied to Mylar on commercial coater.
  • a volatile flammable organic solvent such as methanol or acetone
  • Illustrative examples of the aforementioned antistatic layer materials include metal halides such as potassium iodide, 99 percent pure A.C.S. reagent, sodium iodide anhydrous, 99 + percent pure, lithium bromide, anhydrous, 99 + percent, zinc chloride A.C.S. reagent grade, magnesium chloride anhydrous, mercuric chloride, 99 + percent A.C.S. reagent grade, cadmium chloride, anhydrous A.C.S. reagent grade, complexed with polymers as indicated herein, or urea compounds such as urea, 99.9 percent pure Gold label, thiourea, 99 + percent pure A.C.S.
  • metal halides such as potassium iodide, 99 percent pure A.C.S. reagent, sodium iodide anhydrous, 99 + percent pure, lithium bromide, anhydrous, 99 + percent, zinc chloride A.C.S. reagent grade, magnesium chloride anhydrous
  • reagent Gold label urea monohydrochloride, urea phosphate, 98 percent pure and urea sulfate, 97 percent pure, complexed with polymers.
  • the metal halides and urea compounds are commercially available with Aldrich Chemicals being one of the sources.
  • the antistatic layer includes polymers containing oxyalkylene units such as poly(methylene oxide) with a melting point of 175°C, poly(ethylene oxide) with an average molecular weight of from 1.0 x 10 3 to about 1.0 x 10 6 , melting point 65 °C, poly-(propylene oxide) with an average molecular weight of from about 1.0 to 10 3 to about 1.0 x 10 4 , poly-(tertramethylene oxide) with an average molecular weight of from about 650 to about 1.0 x 10 4 , poly-(ethylene adipate) with an average molecular weight of from about 5.0 x 10 3 to about 5.0 x 10 4 with a melting point of 55 C, poly(ethylene succinate) with an average molecular weight of from about 5.0 x 10 3 to about 5.0 x 10 4 , poly-(epichlorohydrin) with an average molecular weight of from about 5.0 x 10 4 to about 1.0 x 10 6 , ethylene oxide/propylene oxide
  • Illustrative examples of the resin binders present in the antistatic layer in combination with the antistatic complexes of metal halides, and urea compounds with polymers containing oxyalkylene units include hydroxypropylmethyl cellulose phthalate with free phthalic acid from about 0.5 to about 0.7 percent by weight, carboxybenzoyl groups from about 21.5 to about 32.25 percent by weight, methoxyl groups from about 19.85 to about 22.25 percent by weight, hydroxypropyl groups from about 6.15 to about 7.45 percent by weight; hydroxypropylmethyl cellulose acetate succinate with a methoxyl content from about 20.0 to about 26.0 percent by weight, hydroxypropyl content from about 5.0 to about 10.0 percent by weight, acetyl content from about 5.0 to about 14.0 percent by weight, succinoyl content from about 18.0 to about 4 percent by weight, cellulose acetate hydrogen phthalate with free phthalic acid from about 3.5 to about 21.0 percent by weight, carboxybenzoyl groups from
  • the preferred binders can be vinyl alcohol/vinyl acetate copolymer, hydroxypropyl methyl cellulose, poly(2-hydroxyethyl methacrylate), and hydroxypropyl methyl cellulose phthalate primarily because of their compatibility with the antistatic complexes, low costs in many instances, and commercial availability.
  • the adhesive layer polymers include poly(ethylene) (#042, Scientific Polymer Products), poly(propylene) atactic (#780, Scientific Polymer Products), poly(1-butene) (#337, Scientific Polymer Products); chlorinated poly-(ethylene) (#327, chlorine content 48 percent by weight, Scientific Polymer Products); chlorinated poly(propylene) (#117, chlorine content 65 percent by weight, Scientific Polymer Products); chlorosulfonated poly(ethylene) (#107, chlorine content 43 percent by weight, sulfur content 1.1 percent by weight as chlorosulfone, Scientific Polymer Products); styrene/isoprene (styrene content 70 percent by weight #18351 Polysciences); styrene/isobutylene (styrene content 70 percent by weight); styrene/ethylene butylene, styrene content 29 percent by weight (Kraton 1652, Shell Company); ethylene/vinyl acetate (#785, vinylacetate content 50
  • antistatic layer in contact with the adhesive layer include blends of poly-(ethylene oxide) (Poly OXWSRN-3000 Union Carbide) or poly(propylene oxide) (#822, Scientific polymer products), ethylene oxide/propylene oxide block copolymer (Tetronic 50R8, BASF Corporation), 99.5 percent by weight, and potassium iodide, sodium iodide (Aldrich Chemicals) or lithium bromide (Aldrich Chemicals) or zinc chloride (Aldrich Chemicals), 0.5 percent by weight; blends of poly(oxyethylene sorbitan monolaurate) (Alkamuls PS ML-4 Alkaril Chemicals), poly-(oxyethylene tallow amine) (Alkaminox T-5, Alkaril Chemicals) (Icomeen T-15, ICI Chemicals), castor oil ethoxylates (Alkasurf CO-10, Alkaril Chemicals) poly(ethylene glycol mono laurate) (Alkamuls 400-ML) 90 percent by
  • the antistatic layer coatings can contain in an effective amount of, for example, from about 0.5 to about 10 percent by weight of colloidal silica particles, a carbonate, such as calcium carbonate, and the like primarily for the purpose of transparency traction during the feeding process.
  • Illustrative examples of supporting substrates with an effective thickness of, for example, from about 50 microns to about 150 microns, and preferably of a thickness of from about 75 microns to about 125 microns that may be selected for the transparencies of the present invention include Mylar, commercially available from E.I. DuPont; Melinex, commercially available from Imperial Chemical Inc.; Celenar, commercially available from Celanese, Inc.; polycarbonates, especially Lexan; polysulfones, cellulose triacetate; poly(vinyl chlorides), cellophane and poly(vinyl fluorides); and the like, with Mylar being particularly preferred in many embodiments because of its availability and lower costs.
  • Filler components in various effective amounts such as, for example, from about 0.5 to about 10 and preferably from about 1 to about 5 weight percent can be included in the coating as indicated herein.
  • examples of fillers include colloidal silicas preferably present, for example, in one embodiment in an amount of 1 weight percent (available as Syloid 74 from W.R. Grace Company); calcium carbonate, (Microwhite Sylacauga Calcium Products) titanium dioxide (Rutile NL Chem. Canada Inc.), and the like. While it is not desired to be limited by theory, it is believed that the primary purpose of the fillers is as a slip component for the transparency traction during the feeding process.
  • the aforementioned coatings can be present on the supporting substrates, for example each exposed surface thereof such as Mylar, in various thicknesses depending on the coatings selected and the other components utilized; however, generally the total thickness of the coatings is from about 2 to about 15 microns, and preferably from about 3 to about 10 microns.
  • these coatings can be applied by a number of known techniques including reverse roll, extrusion and dip coating processes. In dip coating, a web of material to be coated is transported below the surface of the coating material by a single roll in such a manner that the exposed site is saturated, followed by the removal of any excess by a blade, bar or squeeze rolls.
  • the premetered material is transferred from a steel applicator roll to the web material moving in the opposite direction on a backing roll.
  • Metering is performed in the gap precision-ground stainless steel rolls.
  • the metering roll is stationary or is coating slowly in the opposite direction of the applicator roll.
  • slot extrusion coating there is selected a slot die to apply coating materials with the die lips in close proximity to the web of material to be coated. Once the desired amount of coating has been applied to the web, the coating is dried at 70 to 100° C in an air dryer.
  • the xerographic transparencies of the present invention are prepared by providing a supporting substrate such as Mylar in a thickness of from about 75 to about 125 microns; and applying to each side of the substrate by known dip coating process, in a thickness of from about 3 to 15 microns, a coating composition comprised of an adhesive layer overcoated with an antistatic layer as illustrated herein. Thereafter, the substate and coatings are air dried at 25 C for 60 minutes in a fume hood equipped with adjustable volume exhaust system. The resulting transparency can be utilized in various imaging apparatuses including the xerographic imaging apparatus such as those available commercially as the Xerox Corporation 1005TM and wherein there results images thereon, and the like.
  • uncoated polyester of a thickness of 100 microns (/1.m) tested on a static charge analyzer accepted a charge of about 1,200 volts which did not decay with light.
  • poly(ethylene oxide) was replaced with a block copolymer of ethylene oxide/propylene oxide (Tetronic 50R8, BASF Corporation) and coated on polyester from a 10 percent by weight solution in pure methanol.
  • This coating accepted a charge of 1,260 volts which discharged very slowly on exposure to light and approached 400 volts, which residual charge stayed on the transparency.
  • 0.1, 0.2, and 0.4 percent by weight of potassium iodide to the aforementioned coating solution of ethylene oxide/propylene oxide block copolymer and coating these on a polyester, tranparencies were obtained which accepted charges of 700, 410 and 210 volts, respectively.
  • blends of vinyl pyrrolidone/vinyl acetate copolymer which when coated on polyester alone accepts a charge of 1,180 volts without discharging (#368, Scientific Polymer Products) and poly(ethylene glycol monooleate) (Alkamuls 600-MO, Alkaril Chemicals) a poor antistat in proportions of 90:10, 80:20, 70:30 (in 5 percent concentration) in methanol were coated on polyester sheet and tested for their charging/discharging characteristics. These three transparencies charged to about 1,340 volts, but discharged to 1,300, 1,200, 1,080 volts as the concentration of poly(ethylene glycol monooleate) increased from 10 to 20 to 30 percent by weight in the blend.
  • two blends of vinyl pyrrolidone/vinyl acetate copolymer were prepared with an alkanol amide (Alkamide 2104, Alkaril Chemicals) in proportions of 90:10 and 70:30, respectively, in methanol (5 percent by weight) and coated on the above polyester. These transparencies charged to 1,180 and 680 volts and discharged instantaneously. On incorporation of 2.5, 3.5, 4.5 and 7.0 percent potassium iodide to the above blends, and coating them on polyester, transparencies were provided with the charging levels lowered to 800, 630, 450, 340 in the 90:10 blend and to 160, 130, 100 and 80 volts in the 70:30 blend.
  • Alkamide 2104 Alkaril Chemicals
  • alkamide 2104 can be selected to charge vinyl pyrrolidone/vinyl acetate copolymer to a level of 680 volts whereas if 3.5 percent by weight of potassium iodide is added to the blend, one needs only 10 percent by weight of alkamide 2104 in this embodiment. These results further demonstrate that the presence of potassium iodide can enhance the performance of an oxyalkylene unit containing antistat.
  • the performance of poly(ethylene oxide) (POLYOX WSRN-3000) coated film which was shown to accept a charge of 1,200 volts and discharge completely with light, was observed to be improved when a 92:8 by weight blend of poly(ethylene oxide) and urea coated on polyester yielded transparencies which charged to 400 volts only and discharged completely.
  • POLYOX WSRN-3000 poly(ethylene oxide) coated film
  • the oxyalkylene containing polymers can also be made better antistats in the presence of urea containing compounds.
  • These antistatic complexes of oxyalkylene containing polymers with potassium iodide and/or urea can be incorporated in resin binders or used alone for transparency applications as indicated herein.
  • the imaging technique in known ink jet printing involves, for example, the use of one or more ink jet assemblies connected to a pressurized source of ink, which is comprised of water, glycols, and a colorant such as magenta, cyan, yellow or black dyes.
  • a pressurized source of ink which is comprised of water, glycols, and a colorant such as magenta, cyan, yellow or black dyes.
  • Each individual ink jet includes a very small orifice usually of a diameter of 0.0024 inch, which is energized by magneto restrictive piezoelectric means for the purpose of emitting a continuous stream of uniform droplets of ink at a rate of 33 to 75 kilohertz.
  • This stream of droplets is desirably directed onto the surface of a moving web of, for example, the transparencies of the present invention, which stream is controlled to permit the formation of printed characters in response to video signals derived from an electronic character generator and in response to an electrostatic deflection system.
  • a latent image generated on a photoconductive member a toner composition (dry or liquid) of resin particles and pigment particles.
  • a suitable substrate such as natural cellulose, the transparencies of the present invention, or plastic paper and affixed thereto by, for example, heat, pressure or combination thereof.
  • a printer such as Roland PR-1012 is connected to an IBM-PC computer loaded with a screen/printer software specially supplied for the printer. Any graphic images produced by the appropriate software on the screen can be printed by using the print screen key on the computer keyboard.
  • the ink ribbons used in dot matrix printers are generally comprised of Mylar coated with blends of carbon black with reflex blue pigment dispersed in an oil, such as rape seed oil, and a surfactant, such as lecithin.
  • Other correctable ribbons which are also used in typewriter printing can be selected and are usually comprised of Mylar coated with blends of soluble nylon, carbon black and mineral oil.
  • the system consists of two major components: an optical sensor and a data terminal.
  • the optical sensor employs a 6 inch integrating sphere to provide diffuse illumination and 8 degrees viewing. This sensor can be used to measure both transmission and reflectance samples. When reflectance samples are measured, a specular component such as glass was included.
  • a high resolution full dispersion, grating monochromator was used to scan the spectrum from 380 to 720 nanometers.
  • the data terminal features a 12 inch CRT display, numerical keyboard for selection of operating parameters, and the entry of tristimulus values; and an alphanumeric keyboard for entry of product standard information.
  • a transparent substrate material for receiving or containing an image comprised of a supporting substrate, an ink toner receiving coating composition present on each of surface of the substrate and comprised of an adhesive layer, and an antistatic layer contained on both surfaces of the adhesive layer, which antistatic layer is comprised of complexes of metal halides, or urea compounds both with polymers containing oxyalkylene units; a transparent substrate material for receiving or containing an image comprised of a supporting substrate, an ink toner receiving coating composition present on each of surface of the substrate and comprised of an adhesive layer, and an antistatic layer contained on both outer surfaces of the adhesive layer, which antistatic layer is comprised of complexes of metal halides or urea compounds both with polymers containing oxyalkylene units; a transparent substrate material for receiving an image comprised of a supporting substrate, an ink toner receiving coating composition on two surfaces of the substrate and comprised of an adhesive layer, and antistatic layers in contact with each surface of the adhesive, and comprised of complexe
  • These sheets (10) were then coated with an antistatic polymer layer by affecting a dip coating of these sheets into a solution comprised of a mixture of poly(ethylene oxide) (Poly OX WSRN-3000, Union Carbide), 99.5 percent by weight, and potassium iodide, 0.5 percent by weight, which solution was present in a concentration of 0.5 percent by weight in methanol. Subsequent to air drying for 60 minutes at 25 C and monitoring the difference in weight prior to and subsequent to coating, the coated sheets had present on each exposed surface (two) of the adhesive layer, or both sides, 50 milligrams, 0.5 micron in thickness, of the antistatic layer.
  • a solution comprised of a mixture of poly(ethylene oxide) (Poly OX WSRN-3000, Union Carbide), 99.5 percent by weight, and potassium iodide, 0.5 percent by weight, which solution was present in a concentration of 0.5 percent by weight in methanol.
  • the coated sheets had present on each exposed surface (two) of the adhesive layer, or both
  • the prepared coated sheets were then fed individually into a Xerox Corporation 1075TM imaging apparatus containing a carbon black toner composition, (styrene butadiene, 91/9, 90 weight percent, carbon black Regal 330@, 10 weight percent) and there were obtained images with an average optical density values of 1.60 (black). These images could not be hand wiped or lifted with a scotch tape 60 seconds subsequent to their preparation.
  • a carbon black toner composition styrene butadiene, 91/9, 90 weight percent, carbon black Regal 330@, 10 weight percent
  • These sheets (20) were then coated with an antistatic polymer layer by affecting a dip coating of these sheets into a solution comprised of a mixture of poly(2-hydroxyethyl methacrylate) (Scientific Polymer Products), 65 percent by weight, poly-(ethylene oxide) (Poly OX WSRN-3000, Union Carbide), 32 percent by weight, and sodium iodide (Aldrich Chemicals), 2 percent by weight, colloidal silica, 1 percent by weight, which solution was present in a concentration of 3 percent by weight in methanol.
  • a solution comprised of a mixture of poly(2-hydroxyethyl methacrylate) (Scientific Polymer Products), 65 percent by weight, poly-(ethylene oxide) (Poly OX WSRN-3000, Union Carbide), 32 percent by weight, and sodium iodide (Aldrich Chemicals), 2 percent by weight, colloidal silica, 1 percent by weight, which solution was present in a concentration of 3 percent by weight in methanol.
  • the coated sheets had present on each exposed side of the adhesive layer, 300 milligrams, 3 microns in thickness, of the antistatic layer.
  • Ten of these sheets were fed into a Xerox Corporation 1025TM imaging apparatus containing the carbon black toner composition of Example I.
  • the average optical density of the 1025TM images was 1.30. These images could not be handwiped or lifted with a scotch tape 60 seconds subsequent to their preparation.
  • the remaining 10 sheets were fed individually into a Xerox Corporation 4020TM color ink jet printer having incorporated therein four separate developer inks, commercially available from Sharp Inc. and believed to be comprised of water, 92 percent by weight, ethylene glycol, 5 percent by weight, and a magenta, cyan, yellow and black colorant, respectively, 3 percent by weight, and there were obtained images with an average optical density values of 1.70 (black), 1.35 (magenta), 1.50 (cyan) and 0.85 (yellow).
  • the coated sheets had present on each exposed side of the adhesive layer 300 milligrams, 3 microns in thickness, of the antistatic polymer layer in contact with the adhesive ethylene/vinyl acetate copolymer layer. These sheets were then fed into a Xerox 4020TM color ink jet printer, and there were obtained images with an average optical density values of 1.65 (black), 1.40 (magenta), 1.55 (cyan) and 0.80 (yellow).
  • These sheets (10) were then coated with an antistatic polymer layer by affecting a dip coating of these sheets into a solution comprised of a mixture of vinyl alcohol/vinyl acetate copolymer (with a vinyl alcohol content of 18 percent by weight), 60 percent by weight, ethylene oxide/propylene oxide block copolymer (Tetronic 50R8, BASF Corporation), 38 percent by weight, potassium iodide (Aldrich Chemicals), 2 percent by weight, which solution was present in a concentration of 1 percent by weight in methanol.
  • a solution comprised of a mixture of vinyl alcohol/vinyl acetate copolymer (with a vinyl alcohol content of 18 percent by weight), 60 percent by weight, ethylene oxide/propylene oxide block copolymer (Tetronic 50R8, BASF Corporation), 38 percent by weight, potassium iodide (Aldrich Chemicals), 2 percent by weight, which solution was present in a concentration of 1 percent by weight in methanol.
  • the coated sheets had present on each side, 100 milligrams, 1 micron in thickness, of the antistatic polymer layer in contact with the adhesive chlorinated poly(isoprene) layer.
  • These sheets were then fed into a Xerox Corporation 1005TM color imaging apparatus and images were obtained on the aforementioned transparencies with an average optical density (that is the sum of the optical densities of 10 sheets divided by 10) of 1.80 (black), 0.90 (yellow), 1.50 (cyan) and 1.65 (magenta). These images could not be handwiped or lifted with scotch tape (Minnesota Minning and Manufacturing) 60 seconds subsequent to their preparation.
  • the coated sheets had present on each side (both sides that are exposed) of the adhesive layer, 100 milligrams, 1 micron in thickness, of the antistatic layer. These sheets were then fed individually into a Xerox Corporation 1025TM imaging apparatus containing a carbon black toner composition. The average optical density of these images was 1.25. These images could not be hand wiped or lifted with a scotch tape 60 seconds subsequent to their preparation.

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0588724A1 (fr) * 1992-09-18 1994-03-23 Minnesota Mining And Manufacturing Company Feuille réceptrice d'images pour copieurs sur papier ordinaire
EP0588723A1 (fr) * 1992-09-18 1994-03-23 Minnesota Mining And Manufacturing Company Support d'impression d'image transparent en solution aqueuse pour copieurs à papier ordinaire
US5302439A (en) * 1993-03-19 1994-04-12 Xerox Corporation Recording sheets
WO1995018992A1 (fr) * 1994-01-07 1995-07-13 Minnesota Minning And Manufacturing Company Couche receptrice de toner electrostatique en thermoplastique modifie au caoutchouc
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EP0678546A2 (fr) * 1994-04-20 1995-10-25 Imperial Chemical Industries Plc Film polymère
EP0695789A1 (fr) * 1994-08-01 1996-02-07 Hitachi Maxell Ltd. Feuille d'impression dont les dépÔts peuvent être enlevés aisement
US6051355A (en) * 1997-08-01 2000-04-18 Agfa-Gevaert, N. V. Receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups
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Families Citing this family (44)

* Cited by examiner, † Cited by third party
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DE69222458T2 (de) * 1991-04-05 1998-02-05 Asahi Glass Co Ltd Aufzeichnungsblatt für elektrostatische Bildübertragung
DE69215189T2 (de) * 1991-10-04 1997-04-17 Minnesota Mining & Mfg Neue Rezeptoren für Farbstoffübertragung
US5451466A (en) * 1993-03-19 1995-09-19 Xerox Corporation Recording sheets
US5451458A (en) * 1993-03-19 1995-09-19 Xerox Corporation Recording sheets
US5521002A (en) * 1994-01-18 1996-05-28 Kimoto Tech Inc. Matte type ink jet film
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EP0685345B1 (fr) * 1994-05-25 1998-09-09 Asahi Glass Company Ltd. Feuille d'enregistrement et enregistrement
US5939193A (en) * 1994-12-23 1999-08-17 Rexam Graphics Inc. Overhead transparency for color laser printers and copiers
US5906905A (en) * 1996-01-11 1999-05-25 Xerox Corporation Simulated photographic-quality prints using a transparent substrate containing a wrong reading image and a backing sheet containing an ultraviolet light absorber
US5660962A (en) * 1996-01-11 1997-08-26 Xerox Corporation Simulated photographic-quality prints using a transparent substrate containing a wrong reading image and a backing sheet containing an adhesive coating which enhances image optical density and a hydrophilic wetting agent
US5665504A (en) * 1996-01-11 1997-09-09 Xerox Corporation Simulated photographic-quality prints using a plasticizer to reduce curl
US5714287A (en) * 1996-01-11 1998-02-03 Xerox Corporation Simulated photographic-quality prints using a transparent substrate containing a wrong reading image and a backing sheet containing an adhesive coating which enhances image optical density
US5693437A (en) * 1996-01-11 1997-12-02 Xerox Corporation Simulated photographic-quality prints with a hydrophobic scuff resistant coating which is receptive to certain writing materials
US5663030A (en) * 1996-01-24 1997-09-02 Xerox Corporation Electrostatic imaging process
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US5624743A (en) * 1996-02-26 1997-04-29 Xerox Corporation Ink jet transparencies
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US5683793A (en) * 1996-06-03 1997-11-04 Xerox Corporation Ink jet transparencies
US5693410A (en) * 1996-09-03 1997-12-02 Xerox Corporation Ink jet transparencies
US5756226A (en) * 1996-09-05 1998-05-26 Sterling Diagnostic Imaging, Inc. Transparent media for phase change ink printing
US6086700A (en) 1996-09-05 2000-07-11 Agfa-Gevaert N.V. Transparent media for phase change ink printing
US5965206A (en) * 1996-09-16 1999-10-12 Ciba Specialty Chemicals Corporation Antistatic composition
US5795696A (en) * 1996-10-02 1998-08-18 Xerox Corporation Laminatable backing substrates containing paper desizing agents
US5856021A (en) * 1997-02-06 1999-01-05 Eastman Kodak Company Toner-receptive media for digital offset printing
US5846637A (en) * 1997-05-07 1998-12-08 Xerox Corporation Coated xerographic photographic paper
WO1999018159A1 (fr) * 1997-10-06 1999-04-15 Alza Corporation Composition moulable par injection et produit manufacture a base de cette composition
US6180255B1 (en) 1998-02-05 2001-01-30 Agfa Gevaert N.V. Structured media for phase change ink printing
US6099956A (en) * 1998-07-17 2000-08-08 Agfa Corporation Recording medium
US6096443A (en) * 1998-07-17 2000-08-01 Xerox Corporation Transparencies
US5985929A (en) * 1998-11-05 1999-11-16 Kern; Jerome Cold chemical sterilant
US6258451B1 (en) 1998-11-20 2001-07-10 Agfa Gevaert N.V. Recording medium
US6210816B1 (en) 1999-03-26 2001-04-03 Xerox Corporation Translucent xerographic recording substrates
JP4667569B2 (ja) * 2000-09-13 2011-04-13 三井化学株式会社 ヒートシール性コート剤、およびそれを塗工してなるヒートシール性多層構造体
JP4000246B2 (ja) * 2001-04-06 2007-10-31 富士フイルム株式会社 インクジェット記録用シートの製造方法
JP3901534B2 (ja) * 2001-10-11 2007-04-04 株式会社クレハ 制電性樹脂組成物
KR20010109514A (ko) * 2001-11-19 2001-12-10 손진기 영구적인 대전방지성을 갖는 아크릴 패널의 제조방법
DE102005001616A1 (de) * 2005-01-12 2006-07-20 Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg Antistatische Oberflächenausrüstung
US7915334B2 (en) * 2006-11-13 2011-03-29 Kanzaki Specialty Papers, Inc. Dual purpose receiver sheet
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EP2567812B1 (fr) * 2011-09-12 2015-06-17 Agfa-Gevaert Laminés de sécurité à base Pet-C et documents
US9475930B2 (en) 2012-08-17 2016-10-25 Metabolix, Inc. Biobased rubber modifiers for polymer blends
EP3004225A1 (fr) 2013-05-30 2016-04-13 Metabolix, Inc. Mélanges de recyclat
CN106459544B (zh) 2014-03-27 2021-10-01 Cj 第一制糖株式会社 高度填充的聚合物体系
CN116023696B (zh) * 2021-10-25 2024-08-30 浙江欧仁新材料有限公司 抗静电离型膜的制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199874A1 (fr) * 1985-02-25 1986-11-05 The Mead Corporation Feuille pour l'enregistrement à jet d'encre comportant une couche réceptive d'encre contenant de l'oxyde de polyéthylène
EP0240147A2 (fr) * 1986-03-31 1987-10-07 Minnesota Mining And Manufacturing Company Feuilles transparentes pour photocopieurs électrostatiques
DE3625188A1 (de) * 1986-07-25 1988-01-28 Bayer Ag Verfahren zur antistatischen ausruestung von polyamiden/polyimiden, antistatisch ausgeruestete werkstoffe und ihre verwendung
EP0332183A2 (fr) * 1988-03-11 1989-09-13 E.I. Du Pont De Nemours And Company Transparents électrostatiques contenant un support en polyester

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE790087A (fr) * 1971-10-13 1973-04-13 Eastman Kodak Co Procede de traitement d'une pellicule destinee notamment a la fabrication de produits photographiques
US4013696A (en) * 1973-07-25 1977-03-22 Eastman Kodak Company Element comprising a coating layer containing a mixture of a cationic perfluorinated alkyl and an alkylphenoxy-poly(propylene oxide)
US3993549A (en) * 1974-07-12 1976-11-23 W. R. Grace & Co. Curable solid adducts of polyene-polythiol compositions with urea
JPS5942864B2 (ja) * 1979-04-13 1984-10-18 京セラミタ株式会社 投影用原稿の作成方法及びそれに用いる静電写真用転写フイルム
US4480003A (en) * 1982-09-20 1984-10-30 Minnesota Mining And Manufacturing Company Construction for transparency film for plain paper copiers
US4489122A (en) * 1982-10-13 1984-12-18 Minnesota Mining And Manufacturing Company Transparencies for electrostatic printing
US4637974A (en) * 1983-04-15 1987-01-20 Weber Marking Systems, Inc. Xerographic copying on a transparent sheet
US4526847A (en) * 1983-04-15 1985-07-02 Weber Marking Systems, Inc. Image receiving transparency and method of making
US4542095A (en) * 1984-07-25 1985-09-17 Eastman Kodak Company Antistatic compositions comprising polymerized alkylene oxide and alkali metal salts and elements thereof
US4547405A (en) * 1984-12-13 1985-10-15 Polaroid Corporation Ink jet transparency
US4592954A (en) * 1985-01-25 1986-06-03 Xerox Corporation Ink jet transparencies with coating compositions thereover
US4997697A (en) * 1989-06-29 1991-03-05 Xerox Corporation Transparencies

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199874A1 (fr) * 1985-02-25 1986-11-05 The Mead Corporation Feuille pour l'enregistrement à jet d'encre comportant une couche réceptive d'encre contenant de l'oxyde de polyéthylène
EP0240147A2 (fr) * 1986-03-31 1987-10-07 Minnesota Mining And Manufacturing Company Feuilles transparentes pour photocopieurs électrostatiques
DE3625188A1 (de) * 1986-07-25 1988-01-28 Bayer Ag Verfahren zur antistatischen ausruestung von polyamiden/polyimiden, antistatisch ausgeruestete werkstoffe und ihre verwendung
EP0332183A2 (fr) * 1988-03-11 1989-09-13 E.I. Du Pont De Nemours And Company Transparents électrostatiques contenant un support en polyester

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 14, no. 52 (M-928)(3995) 30 January 1990 & JP-A-1 280 581 ( FUJI PHOTO FILM CO LTD ) 10 November 1989 *
PATENT ABSTRACTS OF JAPAN vol. 8, no. 199 (C-242)(1636) 12 September 1984 & JP-A-59 091 141 ( KOJIN K.K. ) 25 May 1984 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU669378B2 (en) * 1992-09-18 1996-06-06 Minnesota Mining And Manufacturing Company Water-based transparent image recording sheet for plain paper copiers
EP0588723A1 (fr) * 1992-09-18 1994-03-23 Minnesota Mining And Manufacturing Company Support d'impression d'image transparent en solution aqueuse pour copieurs à papier ordinaire
EP0588724A1 (fr) * 1992-09-18 1994-03-23 Minnesota Mining And Manufacturing Company Feuille réceptrice d'images pour copieurs sur papier ordinaire
AU669553B2 (en) * 1992-09-18 1996-06-13 Minnesota Mining And Manufacturing Company Image-receptive sheets for plain paper copiers
US5302439A (en) * 1993-03-19 1994-04-12 Xerox Corporation Recording sheets
EP0616262A2 (fr) * 1993-03-19 1994-09-21 Xerox Corporation Feuilles d'enregistrement
EP0616262A3 (fr) * 1993-03-19 1995-08-02 Xerox Corp Feuilles d'enregistrement.
EP0663620A2 (fr) * 1993-10-19 1995-07-19 Minnesota Mining And Manufacturing Company Feuille d'enregistrement d'images, transparente à base d'eau
EP0663620A3 (fr) * 1993-10-19 1995-08-02 Minnesota Mining And Manufacturing Company Feuille d'enregistrement d'images, transparente à base d'eau
WO1995018992A1 (fr) * 1994-01-07 1995-07-13 Minnesota Minning And Manufacturing Company Couche receptrice de toner electrostatique en thermoplastique modifie au caoutchouc
EP0678546A3 (fr) * 1994-04-20 1996-03-06 Ici Plc Film polymère.
EP0678546A2 (fr) * 1994-04-20 1995-10-25 Imperial Chemical Industries Plc Film polymère
US5882800A (en) * 1994-04-20 1999-03-16 Imperial Chemical Industries Plc Polymeric film having an antistatic coating layer
EP0695789A1 (fr) * 1994-08-01 1996-02-07 Hitachi Maxell Ltd. Feuille d'impression dont les dépÔts peuvent être enlevés aisement
US5876847A (en) * 1994-08-01 1999-03-02 Hitachi Maxell, Ltd. Reusable printing sheet
US6051355A (en) * 1997-08-01 2000-04-18 Agfa-Gevaert, N. V. Receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups
EP1702762A1 (fr) * 2005-03-14 2006-09-20 Ricoh Company, Ltd. Matériau d'enregistrement sensible à la chaleur
US7419935B2 (en) 2005-03-14 2008-09-02 Ricoh Company, Ltd. Heat-sensitive recording material

Also Published As

Publication number Publication date
DE69125421D1 (de) 1997-05-07
JPH04232773A (ja) 1992-08-21
JP3201486B2 (ja) 2001-08-20
DE69125421T2 (de) 1997-07-17
CA2041911A1 (fr) 1991-12-28
CA2041911C (fr) 1998-12-22
EP0463400B1 (fr) 1997-04-02
US5202205A (en) 1993-04-13

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